CN102336850A - Catalyst for catalyzing chain shuttle polymerization of ethylene and application thereof - Google Patents
Catalyst for catalyzing chain shuttle polymerization of ethylene and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for catalyzing chain shuttle polymerization of ethylene and application thereof. The catalyst mainly comprises a main catalyst, a cocatalyst and a chain shuttle agent, wherein the main catalyst agent is a loaded bis(imino)pyridyl iron complex; the cocatalyst is modified methylaluminoxane; the chain shuttle agent is diethylzinc; the bis(imino)pyridyl iron complex is prepared by loading the bis(imino)pyridyl iron complex onto a modified magnesium chloride carrier; in the loaded catalyst, the molar ratio of the cocatalyst to the bis(imino)pyridyl iron complex is (100-500):1; and the molar ratio of the chain shuttle agent to the bis(imino)pyridyl iron complex is (300-800):1. When the catalyst is applied to an ethylene chain shuttle polymerization reaction, the polymerization reaction temperature can be remarkably increased, high activity is kept at the temperature 50-70 DEG C, the molecular weight of a polyethylene product is increased, and ethylene and terminal group-functionalized ethylene with narrow molecular weight distribution can be obtained.
Description
Technical field
The invention belongs to the Polymer Synthesizing field, be specifically related to a kind of catalyzed ethylene chain shuttle back and forth polymeric catalyzer and application thereof.
Background technology
Vilaterm is the general-purpose plastics that has the call in the world, is characterized in low price, and is functional, can be widely used in plastics industry, occupying critical role in industry, agricultural and the daily life; But because Vilaterm is a non-polar material, surface active can be low, caused poly printing and dyeing property, gas permeability and all very poor with the consistency of polar material.These drawbacks limit poly range of application, therefore in the sub polyethylene subchain, introduce polar group or other functional groups, realize that poly functionalization is the important channel of improving Vilaterm performance and purposes.Utilizing the living coordination polymerization of alkene that polar group is introduced Vilaterm segment end is one of method of Vilaterm functionalization.But this method is had relatively high expectations to catalyzer and polymerizing condition, has only back few transition metals catalyzer just can show the characteristic of living polymerization.This is the problem owing to the consistency of catalyzer and functional group in the restriction of reactive polymer end of the chain functionalization chain termination and the living polymerization.And activity of such catalysts center of conventional living polymerization can only produce a polymer chain, so catalytic efficiency (is very low, and polymerization can address the above problem and ethylene chain shuttles back and forth.
The polymerization of shuttling back and forth of alkene chain is that growing chain is transferred on the chain shuttling agent from the chainpropagation center of transition metal; Make transfer reaction temporarily be in dormant state; Growing chain shuttles back and forth to the active site of polycoordination once more fast reversiblely then, continues to take place transfer reaction.Be that the polymer growth chain shuttles between catalyst active center and chain shuttling agent.In the polymerization in homogeneous phase system that chain shuttles back and forth, chainpropagation active site and chain shuttling agent are dissolved in polymerisation medium; Transfer and reverse transfer to guarantee the polyolefine growing chain can be achieved by means of the bimetal intermediate state of alkyl bridged bond.Chain shuttle back and forth on the polymerization requirement chain shuttling agent alkyl or polyolefine growing chain can and Primary Catalysts on the polyolefine growing chain exchange apace, the chain speed of shuttling back and forth will be far longer than rate of chain growth.Chain shuttles back and forth, and chain shuttling agent is indispensable in the polymerization; Use zinc ethyl to be chain shuttling agent generally speaking; This is that simultaneously, Zn – C is also similar with the polarity of Fe – C because bond energy between the carbon-zinc of zinc alkyl(s) and the bond energy between transition metal and the carbon mate most; Therefore the transfer of polyolefine growing chain is suitable with countertransference speed, for the realization that chain exchanges is laid a good foundation.M-C (M is the chain shuttling agent metal) should have high reaction activity and high simultaneously, can further modify through chemical reaction.
The chain polymerization of shuttling back and forth has the single characteristic of molecular weight distribution of conventional active polymerization system; And polyolefin molecular weight can be greater than the molecular weight of deposition during stagnation point; This is by the chain polymeric essence decision of shuttling back and forth, and that is to say that the polymerization of shuttling back and forth of common chain is difficult to prepare and has the higher molecular weight linear polyethylene.Simultaneously, the shuttle back and forth thermostability of system of homogeneous phase pyridine diimine iron catalyst ethylene chain is poor, under comparatively high temps, does not have activity basically.
Domestic and international research is found in recent years, with aluminum alkyls (AlR
3) modified chlorinated magnesium/alcohol (MgCl
2/ nR ￠ OH) MgCl that makes of complex compound
2/ R
nAl (OR ￠)
3-nCarrier comes load homogeneous phase single site catalysts to show many advantages, receive much attention (
Chem. Rev.,
2005, 105:4073-4147.).Through homogeneous phase single site catalysts and MgCl
2/ R
nAl (OR ￠)
3-nCarrier forms strong chemical bond and combines, and can avoid coming off of active site, has the effect at stabilizing active center.At present, not having bibliographical information working load type pyridine diimine iron catalyst ethylene chain to shuttle back and forth both at home and abroad temporarily, polymerization is synthetic has higher molecular weight and narrow molecular weight distributions Vilaterm and an end group functional Vilaterm.
Summary of the invention
The objective of the invention is to the existing homogeneous phase pyridine diimine iron catalyzed ethylene chain catalyzer thermostability of shuttling back and forth not enough; The deficiency that is difficult to synthetic higher molecular weight polyethylene; A kind of catalyzed ethylene chain polymeric catalyzer that shuttles back and forth is provided; This catalyst ethylene chain has high catalytic activity and good thermostability when shuttling back and forth polymerization, be used for synthetic Vilaterm or end group functional Vilaterm with narrower MWD and higher molecular weight.
Another object of the present invention is to provide the said catalyzed ethylene chain polymeric Application of Catalyst of shuttling back and forth.
Above-mentioned purpose of the present invention is achieved through following technical scheme:
A kind of catalyzed ethylene chain polymeric catalyzer that shuttles back and forth is made up of Primary Catalysts, promotor and chain shuttling agent; Said Primary Catalysts is a loading type pyridine diimine iron complex, and said promotor is a modified methylaluminoxane, and said chain shuttling agent is a zinc ethyl; Said loading type pyridine diimine iron complex obtains for the pyridine diimine iron complex loads on the modified chlorinated magnesium carrier; Said pyridine diimine iron complex has following structural formula:
Wherein, said R
1, R
2For Wasserstoffatoms, alkyl, alkoxyl group or contain heteroatom group, X is a halogen;
Said modified chlorinated magnesium carrier is the magnesium chloride/ethanol complex of triethyl aluminum modification, i.e. MgCl
2/ Et
nAl (OEt)
3-n
The mass content of Fe in loading type pyridine diimine iron complex is 0.2 ~ 0.5%;
Said catalyzed ethylene chain shuttles back and forth in the polymeric catalyzer, and the mol ratio of promotor and pyridine diimine iron complex is 100 ~ 500:1; The mol ratio of chain shuttling agent and pyridine diimine iron complex is 300 ~ 800:1.
As a kind of most preferably scheme, in the said pyridine diimine iron complex, R
1Most preferably be ethyl, R
2Most preferably be hydrogen.
As a kind of preferred version; The preparation method of said magnesium chloride support is preferably; Ethanol and Magnesium Chloride Anhydrous are pressed 1 ~ 6:1 mixed in molar ratio, and heating up makes the magnesium chloride dissolving form homogeneous transparent solution, adds normal heptane then and makes magnesium chloride and the abundant dispersion and emulsion of ethanol complex solution; Remove normal heptane and excess ethanol, obtain pulverous magnesium chloride/ethanol complex.
Specifically, the preparation method of said magnesium chloride support does, ethanol is mixed with Magnesium Chloride Anhydrous, and the mol ratio of ethanol and magnesium chloride is 1 ~ 6:1, progressively heats up to make the magnesium chloride dissolving form the solution of homogeneous transparent; Add normal heptane then and make MgCl
2The abundant dispersion and emulsion of/nEtOH solution, reduction vaporization are removed normal heptane and unnecessary ethanol, obtain the MgCl of white powder
2/ nEtOH complex compound.
As a kind of preferred version, the preparation method of said modified chlorinated magnesium carrier is preferably, and magnesium chloride/ethanol complex is mixed with normal heptane; At 0 ~ 25 ℃ of n-heptane solution that slowly adds triethyl aluminum down; Rise to room temperature, reacted 8 ~ 24 hours, filter; Solid obtains the modified chlorinated magnesium of pulverous triethyl aluminum/ethanol complex MgCl through normal heptane washing, drying
2/ Et
nAl (OEt)
3-n
As a kind of preferred version, the preparation method of said loading type pyridine diimine iron complex for the pyridine diimine iron complex is dissolved in toluene solution, makes its solution and MgCl
2/ Et
nAl (OEt)
3-nReacted 2 ~ 5 hours down at 25 ~ 75 ℃, filter, wash with toluene, drying obtains loading on the pyridine diimine iron complex on the modified chlorinated magnesium carrier, and under the nitrogen protection, sealing is preserved.
The pyridine diimine iron complex is through forming covalent linkage between chemical reaction and the modified chlorinated magnesium/ethanol complex of triethyl aluminum; Therefore improve the bonding strength between catalyzer and the carrier; Can avoid effectively that the active site comes off in polymerization process, have thermostability preferably.
Said catalyzed ethylene chain shuttles back and forth the polymeric catalyzer in the application of preparation in the Vilaterm, it is characterized in that, and with toluene solvent, loading type pyridine diimine iron catalyst concentration is 3.0 ~ 6.0 * 10
-4Mol/L carries out 0.5 ~ 3 hour polyreaction under the polymerization pressure of 0.1 ~ 3MPa, 50 ~ 80 ℃ polymeric reaction temperature, obtain Vilaterm.
The Vilaterm of gained is a linear polyethylene, and MWD is 1.13 ~ 1.25.
The application of polymeric catalyzer in preparation terminal hydroxy group Vilaterm of shuttling back and forth of said catalyzed ethylene chain is characterized in that aerating oxygen in the ethene system is a solvent with toluene, and loading type pyridine diimine iron catalyst concentration is 2.0 ~ 5.0 * 10
-4Mol/L carries out 0.5 ~ 3 hour polyreaction under the polymerization pressure of 0.1 ~ 1MPa, 50 ~ 150 ℃ polymeric reaction temperature, obtain the terminal hydroxy group Vilaterm.
Gained terminal hydroxy group Vilaterm is a linear polyethylene, and MWD is 1.13 ~ 1.25.
Compared with prior art, the present invention has following beneficial effect:
The present invention loads on MgCl through chemical b ` with it with the pyridine diimine iron complex
2/ Et
nAl (OEt)
3-nOn the carrier, can reduce of the influence of the functional group of carrier surface, owing to be the valence link effect between carrier and the catalyzer to the active site; Therefore bonded intensity is bigger, can avoid effectively like this that the active site comes off in polymerization process, has thermostability preferably; The said catalyzed ethylene chain polymeric loaded catalyst that shuttles back and forth carrying out ethylene chain when shuttling back and forth polyreaction, still can keep advantages of high catalytic activity more than 50 ℃; Promptly under higher temperature, react; Significantly improve the molecular weight of polyethylene kind product, and make the MWD of products obtained therefrom narrower, thus the quality of raising polyethylene product.
Description of drawings
The terminal hydroxy group Vilaterm hydrogen spectrogram that Fig. 1 makes for the embodiment of the invention 8;
The terminal hydroxy group Vilaterm carbon spectrogram that Fig. 2 makes for the embodiment of the invention 8.
Embodiment
Further explain the present invention below in conjunction with specific embodiment, but embodiment does not do any type of qualification to the present invention.
Embodiment 1: the preparation of pyridine diimine iron complex
Accurate weighing 0.50g (0.30mmol) 2; The 6-diacetyl pyridine adds in the clean 100mL round-bottomed flask; Add absolute ethyl alcohol 40mL successively, mole number doubles 2,2 of the new steaming of 6-diacetyl pyridine, 6-xylidine and a small amount of formic acid (catalyzer); Heated and stirred to alcoholic acid reflux temperature (about 80 ℃), isothermal reaction 6h.The cooling after-filtration goes out deposition (needing the freezing product that makes to separate out), and vacuum-drying obtains yellowish powder 0.84g, is pyridine diimine part productive rate and is about 75%.
In exsiccant Schlenk pipe, add accurate weighing 0.24g (0.50 mmol) synthetic part, add the FeCl of equimolar amount
2* 4H
2O 0.10 g (0.52 mmol) adds THF (THF) 15mL, and reaction system becomes prussian's blueness rapidly, and deepens gradually, stirs 24h (25 ℃) under the room temperature.Vacuum concentration is to a small amount of solvent, with the normal hexane blue deposition that settles out.Filter out deposition, vacuum-drying obtains 0.22g pyridine diimine iron complex, and productive rate is about 78%.
Above all operations all carries out under the condition of anhydrous and oxygen-free.
Embodiment 2:MgCl
2
The preparation process of/nEtOH complex compound
Prop up in mouthful round-bottomed flask bottle at 250 ml that have magnetic agitation, condensing works, add Magnesium Chloride Anhydrous 10.00g under the room temperature successively, absolute ethyl alcohol 20.0mL, progressively heating up then makes the magnesium chloride dissolving form the solution of homogeneous transparent.Add 50mL exsiccant normal heptane and make the abundant dispersion and emulsion of solution, reduction vaporization is removed heptane and unnecessary ethanol then, obtains magnesium chloride/ethanol mixture, the N then of white powder
2The protection lower seal is preserved.
Above all operations all carries out under the condition of anhydrous and oxygen-free.
Embodiment 3:MgCl
2
/ Et
n
Al (OEt)
3-n
The preparation process of carrier
Under nitrogen protection, with the MgCl that makes among the 6.00g embodiment 2
2/ nEtOH joins in the 250mL glass reaction bottle, adds the 50.0mL normal heptane, stirs into slurries, under 0 ℃, slowly adds 20mL AlEt
3N-heptane solution (concentration is 0.25g/mL) slowly rises to room temperature, and reaction 24h filters out liquid then, and solid is with normal heptane washing three times, and reduction vaporization is removed normal heptane, obtains MgCl
2/ AlEt
n(OEt)
3-nPowder.
Embodiment 4:MgCl
2
/ AlEt
n
(OEt)
3-n
The load pyridine diimine iron
The toluene solution (0.05mol/L) of pyridine diimine iron complex among the embodiment 1 added respectively 2gMgCl is housed
2/ AlEt
n(OEt)
3-nIn the reaction flask of carrier; React 4h down at 50 ℃, leave standstill, filter, it is colourless basically that solid is washed till toluene solution with toluene, and reduction vaporization is removed toluene, obtains loading type pyridine diimine iron catalyst fines, N
2Protection is taken out down, and sealing is preserved.
Atom color development spectrum (ICP method): Mg:13.25%, Al:4.70%, Fe:0.27%.
Embodiment 5: the polymerization of shuttling back and forth of loaded catalyst catalyzed ethylene chain
After the reaction flask that has magnetic stick and gas duct that drying is good vacuumizes excluding air, use exsiccant N
2Replace twice.Vacuumize, feed and fill ethene to normal pressure after ethene is replaced 2 times, add the toluene of 45mL, stir, 50 ℃ of constant temperature, press Primary Catalysts then: promotor: the molar ratio of chain shuttling agent=1:300:800 adds MMAO and chain-transfer agent ZnEt
2, the concentration that adds the loading type pyridine diimine iron of 5mL again is 4.8 * 10
-4The toluene suspension of mol/L.At 0.12MPa pressure, carry out under 50 ℃ in the whole polymerization process, stop to feed ethene behind the polymerase 10 .5h, with acidifying methanol solution termination reaction.Polymerisate fully soaks, washs with acidifying ethanol, and vacuum-drying is to constant weight, and the calculating catalytic activity.The polymeric catalytic activity is 1.13 * 10
5G PE/molFe * h, number-average molecular weight is 836 g/mol, MWD is 1.13.
Embodiment 6: the polymerization of shuttling back and forth of loaded catalyst catalyzed ethylene chain
Autoclave is heated to 120
oVacuumized about C four hours, and continued to vacuumize being cooled to room temperature.Charge into ethene and be replaced as normal pressure, add metering toluene solution 90mL successively, press Primary Catalysts: promotor: the molar ratio of chain shuttling agent=1:300:800 adds promotor MMAO and chain-transfer agent ZnEt
2Temperature is controlled at 50 ℃ stirs 3min, the concentration that is injected into the loading type pyridine diimine iron of 10mL is 3.6 * 10
-4The toluene solution of mol/L, the ethylene pressure that raises immediately is to 1MPa.Behind 50 ℃ of following polymerase 10 .5h, at first discharge the pressure of ethene, unload autoclave, with the same termination reaction of normal pressure, and vacuum-drying is to constant weight.The polymeric catalytic activity is 2.12 * 10
6G PE/molFe * h, number-average molecular weight is 970 g/mol, MWD is 1.20.
Embodiment 7: the polymerization of shuttling back and forth of loaded catalyst catalyzed ethylene chain
Press the polymerization method of embodiment 6, polymerization temperature is 70 ℃, and other condition is identical.Catalytic activity is 1.0 * 10
6G PE/molFe * h.Number-average molecular weight is 1670g/mol, and MWD is 1.25.
Comparative Examples 1: the homogeneous catalyst catalyzed ethylene chain polymerization of shuttling back and forth
After the reaction flask that has magnetic stick and gas duct that drying is good vacuumizes excluding air, use exsiccant N
2Replace twice.Vacuumize, feed and fill ethene to normal pressure after ethene is replaced 2 times, add the toluene of 45mL, stir, 30 ℃ of constant temperature, press Primary Catalysts then: promotor: the molar ratio of chain shuttling agent=1:300:800 adds MMAO and chain-transfer agent ZnEt
2, the pyridine diimine iron catalyst concn that adds 5mL again is 4.0 * 10
-4The toluene solution of mol/L.At 30 ℃ polymerization temperature, carry out under the polymerization pressure of 0.12MPa in the whole polymerization process, stop to feed ethene behind the polymerase 10 .5h, with acidifying methanol solution termination reaction.Polymerisate fully soaks, washs with acidifying ethanol, and vacuum-drying is to constant weight, and the calculating catalytic activity.The polymeric catalytic activity is 5.08 * 10
5G PE/molFe * h, number-average molecular weight is 700g/mol, MWD is 1.12.
Comparative Examples 2: the homogeneous catalyst catalyzed ethylene chain polymerization of shuttling back and forth
By the polymerization method of Comparative Examples 1, polymerization temperature is 50 ℃, and other condition is identical.Catalyzer is destroyed, and can't obtain polyethylene product, i.e. the polymerization system catalytically inactive.
Comparative Examples 3: the homogeneous catalyst catalyzed ethylene chain polymerization of shuttling back and forth
Autoclave is heated to vacuumized about 120 ℃ four hours, continue to vacuumize being cooled to room temperature.Charge into ethene and be replaced as normal pressure, add metering toluene solution 95mL successively, press Primary Catalysts: promotor: the molar ratio of chain shuttling agent=1:300:800 adds promotor MMAO and chain-transfer agent ZnEt
2Temperature is controlled at 30 ℃ stirs 3min, the pyridine diimine iron catalyst concentration that is injected into 5mL is 2.5 * 10
-4The toluene solution of mol/L, the ethylene pressure that raises immediately are to 1MPa, and polymerization temperature is 30 ℃.Behind the polymerase 10 .5h, at first discharge the pressure of ethene, unload autoclave, with the same termination reaction of normal pressure, and vacuum-drying is to constant weight.The polymeric catalytic activity is 1.85 * 10
6G PE/molFe * h, number-average molecular weight is 730 g/mol, MWD is 1.18.
Comparative Examples 4: the homogeneous catalyst catalyzed ethylene chain polymerization of shuttling back and forth
By the polymerization method of Comparative Examples 3, polymerization temperature is 50 ℃, and other condition is identical.Catalyzer is destroyed, and can't obtain polyethylene product, i.e. the polymerization system catalytically inactive.
From the foregoing description and Comparative Examples; Can find out that homogeneous catalyst only can have good catalytic activity about 30 ℃, then decompose inactivation more than 50 ℃; Under the identical situation of other condition, its prepared Vilaterm number-average molecular weight is only below 750 g/mol; The described catalyzer of the application is still can keep advantages of high catalytic activity under 50 ~ 70 ℃, and simultaneously, in the identical reaction times, the Vilaterm number-average molecular weight that makes is significantly improved.
Embodiment 8: the loaded catalyst catalyzed ethylene chain synthetic terminal hydroxy group Vilaterm of polymerization and in-situ oxidation coupling that shuttles back and forth
Press the polymerization method of embodiment 5, after stopping to feed ethene, in system, feed exsiccant O subsequently after vacuumizing
2, pressure maintains 0.1MPa, and system temperature rises to 100 ℃, sustained reaction 2h.With acidifying methanol solution termination reaction, through filtering, to wash, vacuum-drying is to constant weight.The polymeric catalytic activity is 4.87 * 10
5G PE/molFe * h, the number-average molecular weight that obtains polymkeric substance is 930 g/mol, MWD is 1.20.Fig. 1's
1H NMR shows that the closed-end efficiency of hydroxyl is about 60%, Fig. 2's
13C NMR shows that what obtain is the terminal hydroxy group Vilaterm.
Claims (9)
1. catalyzed ethylene chain polymeric catalyzer that shuttles back and forth is characterized in that, is made up of Primary Catalysts, promotor and chain shuttling agent; Said Primary Catalysts is a loading type pyridine diimine iron complex, and said promotor is a modified methylaluminoxane, and said chain shuttling agent is a zinc ethyl; Said loading type pyridine diimine iron complex obtains for the pyridine diimine iron complex loads on the modified chlorinated magnesium carrier; Said pyridine diimine iron complex has following structural formula:
Wherein, said R
1, R
2For Wasserstoffatoms, alkyl, alkoxyl group or contain heteroatom group, X is a halogen;
Said modified chlorinated magnesium carrier is the magnesium chloride/ethanol complex of triethyl aluminum modification, i.e. MgCl
2/ Et
nAl (OEt)
3-n
The mass content of Fe in loading type pyridine diimine iron complex is 0.2 ~ 0.5%;
Said catalyzed ethylene chain shuttles back and forth in the polymeric catalyzer, and the mol ratio of promotor and pyridine diimine iron complex is 100 ~ 500:1; The mol ratio of chain shuttling agent and pyridine diimine iron complex is 300 ~ 800:1.
2. the catalyzed ethylene chain polymeric catalyzer that shuttles back and forth according to claim 1 is characterized in that, in the said pyridine diimine iron complex, and R
1Be ethyl, R
2Be hydrogen.
3. the catalyzed ethylene chain polymeric catalyzer that shuttles back and forth according to claim 1; It is characterized in that the preparation method of said magnesium chloride support is that ethanol and Magnesium Chloride Anhydrous are pressed 1 ~ 6:1 mixed in molar ratio; Intensification makes the magnesium chloride dissolving form homogeneous transparent solution; Add normal heptane then and make magnesium chloride and the abundant dispersion and emulsion of ethanol complex solution, remove normal heptane and excess ethanol, obtain pulverous magnesium chloride/ethanol complex.
4. the catalyzed ethylene chain polymeric catalyzer that shuttles back and forth according to claim 1 is characterized in that the preparation method of said modified chlorinated magnesium carrier does; Magnesium chloride/ethanol complex is mixed with normal heptane,, rise to room temperature at 0 ~ 25 ℃ of n-heptane solution that slowly adds triethyl aluminum down; Reacted 8 ~ 24 hours; Filter, solid obtains the modified chlorinated magnesium of pulverous triethyl aluminum/ethanol complex MgCl through normal heptane washing, drying
2/ Et
nAl (OEt)
3-n
5. the said catalyzed ethylene chain of the claim 1 polymeric catalyzer that shuttles back and forth is characterized in that the preparation method of said loading type pyridine diimine iron complex is: the pyridine diimine iron complex is dissolved in toluene solution, makes its solution and MgCl
2/ Et
nAl (OEt)
3-nReacted 2 ~ 5 hours down at 25 ~ 75 ℃, filter, wash with toluene, drying obtains loading on the pyridine diimine iron complex on the modified chlorinated magnesium carrier.
6. the said catalyzed ethylene chain of claim 1 shuttles back and forth the polymeric catalyzer in the application of preparation in the Vilaterm, it is characterized in that, and with toluene solvent, loading type pyridine diimine iron catalyst concentration is 3.0 ~ 6.0 * 10
-4Mol/L carries out 0.5 ~ 3 hour polyreaction under the polymerization pressure of 0.1 ~ 3MPa, 30 ~ 80 ℃ polymeric reaction temperature.
7. application as claimed in claim 6 is characterized in that said Vilaterm is a linear polyethylene, and MWD is 1.13 ~ 1.25.
8. the said catalyzed ethylene chain of claim 1 application of polymeric catalyzer in preparation terminal hydroxy group Vilaterm of shuttling back and forth is characterized in that aerating oxygen in the ethene system is a solvent with toluene, and loading type pyridine diimine iron catalyst concentration is 2.0 ~ 5.0 * 10
-4Mol/L carries out 0.5 ~ 3 hour polyreaction under the polymerization pressure of 0.1 ~ 1MPa, 50 ~ 150 ℃ polymeric reaction temperature.
9. application as claimed in claim 8 is characterized in that, said terminal hydroxy group Vilaterm is a linear polyethylene, and MWD is 1.13 ~ 1.25.
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| CN104877054A (en) * | 2015-05-22 | 2015-09-02 | 浙江大学 | HBPE (hyperbranched polyethylene) functionalized with terminal hydroxyl groups and preparation method thereof |
| CN112724492A (en) * | 2020-12-30 | 2021-04-30 | 嘉兴市嘉誉科技有限公司 | Polyethylene conductive composite material with graphene grafted on surface and preparation method thereof |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
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| CN104877054A (en) * | 2015-05-22 | 2015-09-02 | 浙江大学 | HBPE (hyperbranched polyethylene) functionalized with terminal hydroxyl groups and preparation method thereof |
| CN112724492A (en) * | 2020-12-30 | 2021-04-30 | 嘉兴市嘉誉科技有限公司 | Polyethylene conductive composite material with graphene grafted on surface and preparation method thereof |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
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